Bulletin of the Chemical Society of Japan p. 824 - 830 (1994)
Update date:2022-08-16
Topics:
Mitsuhashi, Tsutomu
Hirota, Hiroshi
Yamamoto, Gaku
Rates of heterolytic decompositions of t-butyl chloride, bromide, iodide, and 2,4-dinitrophenolate have been measured by an NMR method in eight deuterated or undeuterated polar solvents; methanol-d4, ethanol-d6, dimethyl-d6 sulfoxide, N,N-dimethylformamide-d7, acetonitrile-d3, pyridine, nitrobenzene, and acetone-d6.The observed solvent effect is discussed on the basis of cation and anion solvation.With t-butyl halides, the anion solvation due to hydrogen bonding by protic solvents drastically decreases on increasing the radius of halide ions, and thus the differential solvation transferred from anion-solvating methanol to cation-solvating dimethyl sulfoxide is dramatically reversed on going from the chloride to the iodide (kMe2SO-d6/kmethanol-d4 at 60 deg C: t-BuCl, 5E-2; t-BuBr, 6E-1; t-BuI, 7).The 2,4-dinitrophenolate behaves like the iodide.Complicated products are obtained in the decomposition of t-butyl bromide in dimethyl sulfoxide; however, a mechanism involving a bimolecular decomposition process of the bromide is ruled out.During the decomposition od t-butyl iodide in dimethyl sulfoxide, an intermediate salt t-butoxydimethylsulfonium iodide has been detected.The salt decomposes to isobutene, but the process is much slower than the heterolytic decomposition of t-butyl iodide itself at ambient temperature.
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